Detergent composition containing a 3, 5-diaminopyrazine-2.6-dicarboxylic acid derivative



United States Patent Ofitice DETERGENT COMPOSITION CONTAINING A 3.5-

DIAMINOPYRAZINE-2.6-DICARBOXYLIC ACID DERIVATIVE Anthony FenwickDaglish, Cheadle Hnlme, England,

Rodolphe Vonderwahl, Riehen, near Basel, Switzerland, and George ArnoldTillotson, Hale, England, assignors to J. R. Geigy A.-G., Basel,Switzerland No Drawing. Filed May 23, 1958, Ser. N0. 737,215 Claimspriority, application Switzerland May 29, 1957 9 Claims. (Cl. 252-117)The present invention concerns capillary active dispersing and cleansingagents which are characterised by a content of 3.5-bis-(sec.amino)-pyrazine-2.6-dicarboxylic acid amides.

Up to now only a few processes are known for the production of 3.2;5.6-bis (2'.4'-dioxo-l '.2'.3.4'-tetrahydro)1.4'-pyrimidino]-pyrazines which have been given the common name ofbis-alloxazines. According to the literature these processes only givepoor yields because of the side reactions which occur and because of theoften troublesome purification of the crude products due to these sidereactions. Thus for example, Bredereck et a1. (Berichte der deutschenchemischen Gesellschaft, vol 86, page 845 (1953) disclose yields of atmost 45% of the theoretical for the condensation of 2 molecules of 1.3-dimethy1-4.S-diamino-uracil in mineral acid solution while splitting 01fammonium salt, or in vol. 87, page 1268 (1954), give the same yields forthe condensation of one molecule of l.3-dimethyl-4.S-diarnino-uracilwith one molecule of 1.3-dimethyl-alloxan. Also Timmis in US. Patent No.2,581,889 mentions yields of up to 63% of crude 3.2;5.6 bis[(1'.3'-dimethyl-2'.4'-dioxo-1.2.3'.4'- tetrahydro) 1.4 pyrimidino]pyrazine (also called 1.3.1.3'-tetramethyl-bis-alloxazine) for thecondensation of one molecule of l.3-dimethyl-4-amino-S-nitroso-uracilwith one mol of 1.3-dimethyl barbituric acid.

It has now been found that very good yields of 3.5-diamino-pyrazine-2.6-dicarboxylic acid derivatives are obtained if onemol of 1.3-disubstituted 4-amino-uracil is condensed with 1 mol of1.3-disubstituted 4-amino-5- nitroso-uracil while splitting off one molof water and one mol of ammonia to form the corresponding 3.2;5.6-bis-[(2'.4' dioXo l.2'.3'.4 tetrahydro)-1'.4'-pyrimidino] -pyrazine andthis compound is saponified by known methods either direct or in stepsto form derivatives of 3.5-diaminopyrazine-2.6-dicarboxylic acid, ifdesired while modifying free carboxylic groups by amidation.

The 1.3-disubstituted 4-aminoor 4-amino-4-nitrosouracils used accordingto the said process can be symmetrically or unsymmetrically substitutedat the nitrogen atom. As nitrogen substituents both hydrocarbon radicalsand also substituted hydrocarbon radicals of the aliphatic, araliphatic,alicyclic, or aromatic series are used,

r 3,043,780 Patented July 10, 1962 for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, hydroxyethyl, methoxyethyl, ethoxyethyl,'y-methoxypropyl, benzyl, chlorobenzyl, methylbenzyl, cyclohexyl,methyl-cyclohexyl, phenyl, methylphenyl, chlorophenyl, methoxyphenylgroups and starting materials having the same or different substituentsat the nitrogen atom can be condensed.

Saponification of 3.2;5.6-bis [(2'.4 dioxo-1'.2.3'.4-tetrahydro)-1.4'-pyrimidino]-pyrazines in aqueous, alcoholic ororganic/aqueous solution or suspension, with alkalies such as sodium orpotassium hydroxide, leads to corresponding 3.5 bis (sec.amino)-pyrazine-2.6-dicarboxylic acid amides. Under more vigorousconditions, for example in ethanolic potassium hydroxide, the 3.'5-bis-(sec. amino)-pyrazine-2.6-dicarboxylic acid monoamides are formed. Inthese compounds the free carboxyl group can be converted with thionylchloride into the carboxylic acid halide group. Aminolysis of this groupleads to the acid amides. A- technically particularly simple method ofperforming the amidation consists in dissolving the carboxylic acid andthe amine to be introduced in a strong tertiary nitrogen base such aspyridine, homologous pyridines or triethylamines and then stirring ingradually the necessary amount of thionyl chloride or phosphorustrichloride or bromide in the cold. After removal of the nitrogen baseby dilution with water or steam, the 3.5-diaminopyrazine-2.6-dicarboxylic acid diamide is obtained direct. Thefree carbonyl group, which may be in the form of its salts, can also beesterified, for example on treating with dialkyl sulphates.

Other derivatives can be obtained in the aminolysis of the acid chloridegroup by using amines which contain different substituents from thoseoriginally at the nitrogen atom which was linked to the carbonyl group.In this way, in particular also aromatic and heterocyclic amine radicalscan be introduced, for example phenylamino, methylphenylamino,chlorophenylamino, methoxyphenylamino, pyridyl-(2)-a.mino and morpholinogroups. However, it is also possible to introduce hydroxy-alkylaminogroups in this way, for example the monoethanolamide, diethanolamide,2-hydroxypropylamide group, also aminoalkyl carboxylic acid, carboxylicacid ester and carboxylic acid amide groups. Even urea and substitutedurea groups, eg the monophenyl urea group can be introduced in this way.

However, also unsymmetrical amidated end products can be obtained byaminolysis of 3.2;5.6-bis-[(2'.4-dioxol'.2'.3'.4' tetrahydro)pyrimidino-1.4]-pyrazines at a higher temperature with amines such ase.g. benzylamine, whereby only one dioxodetrahydro-pyrimidino ring issplit, and then further hydrolysing with alkalies.

There are, thus, several methods by which it is possible to vary at willthe substitution of the diaminopyrazine dicarboxylic acid amidesaccording to the desired intended use.

3 4 The following sequence illustrates the reactions dethetic, organicnon-soap-anion-active sulphateddetergents scribed: can be used ascleansing agents. These washing agents r r N- o o o N R R2- C-H O NCCO4NH8 6 0:0 C- I H H2O Rr-N C O N-R4 RrN--'C-N 2 NH?" -NR3 0 N 0 I] ll 0 0I II III 9 amlnolysis 1011 R a R -NHz N N\ 'o=0 o 0 H R1HNC CNHRa l I HH v Rz-N o /N H 0H9 RzHN(fi c- :-x X NIH-R5 \.C/ '\N C Rs 9 N 0 NHR4 i)l) or Iv /Ra V N l -COOH -o-01 R1 The derivatives of the3.S-diaminopyrazjne-Z.6-dicarboxylic acid fluoresce in UV-containinglight more or less strongly depending on their composition. The 3.5-bis-(sec. amino)-pyrazine-2.6-dicarboxylic acid amides of the generalFormula IV, wherein X represents an amide radical, in particular theradical of a primary amine are particularly valuable because of theirviolet-blue, blue to green-blue fluorescence.

In the above sequence of reactions, R R R R R -R and R can represent thesame or different organic radicals which have no dyestufl character; Rand R; can represent in addition, hydrogen.

R R R R represent preferably aliphatic radicals such as alkyl andsubstituted alkyl groups, for example methyl, ethyl, n-propyl, n-butyl,hydroxyethyl, fi-hydroxypropyl, methoxyethyl, ethoxyethyl groups,however, they may also represent aralkyl and substituted aralkyl groupssuch as benzyl, methylbenzyl, 'chlorobenzyl, methoxybenzyl groups orcycloaliphatic radicals such as cyclohexyl, methyl-cyclohexyl groups. Rand R can be hydrogen or the same as R in addition R can also be aheterocyclic radical, for example the Z-pyridyl radical or a divalentradical linking two pyrazine radicals, for example an alkylene or adiphenyl alkane radical; it can also represent a carbamyl radical, forexample the phenyl carbamyl radical and thus X can also represent a urearadical or a ureido radical which may possibly be organicallysubstituted. R and R together with the carbamide- N-atom can alsorepresent a heterocyclic radical, for example a piperidino or amorpholino group.

An important application of the present invention is for the improvementof the appearance of textile fibres at any stage of processing bytreating them with aqueous liquors which contain emulisfying, capillaryactive substances in addition to the3.S-diaminopyrazihe-Z.6-dicarboxylic acid amides. In particularlyvaluable compositions according to the present invention, theemulsifying agents also have cleansing properties. The capillary activesubstances can be used as such, or mixed with each other and alsoadmixed with the usual additives (builders). Both the usual watersoluble soaps and also syn-.

can contain substances from the following classes for example:

A. ANION ACTIVE SUBSTANCES naphthols (dodecyl benzene sulphonates,isobut-yl naphthol sulphonates, methyl dinaphthyl sulphonates),benzimidazols having a higher alkyl or alkenyl radical in the2-position, N-phenyl-l.3.5-triazines having a lipophilic hydrocarbonradical of 12 to 18 carbon atoms, succinic acid esters of alkanolshaving 6 to 12 carbon atoms;

(4) Amide-like condensation products of higher fatt acids with:isethiouic acid (Igepon A), taurine and N- methyl taurine (Igepon T).

B. NON-IONOGENIC SUBSTANCES (l) Polyglycol ethers of higher alkanols andhigher fatty acids as well as of alkyl phenols having lipophilichydrocarbon radicals;

(2) Polyglycol ethers of alkanol amides of higher fatty acids.

The following substances can be added either individually or combined tothe washing agents mentioned above: The sodium or potassium salts ofsulphuric acid, hydrochloric acid, carbonic acid, boric acid, silicicacids, phosphoric acids including those which, as 0rth0-phosphoricacids, have less water content; in addition, alkali metal perborates,percarbonate, persulphate; magnesium salts of meta-silicic acid;cellulose methyl or ethyl ethers, alkali metal salts of carboxymethylcellulose (CMC), of

ethylene diamine tetra-acetic acid and similar N-polyacetic wherein eachof R R and R represents a member selected from the group consisting oflower alkyland phenyl-substituted methyl radicals and X represents anamino group, X can be primary amino or the radical of an organic primaryor secondary amine. In the most valuable and therefore preferredcompounds, X is the radical of a primary amine of the aliphatic,phenyl-substituted lower aliphatic, alicyclic, mononuclear isocyc1icaromatic and heterocyclic series.

In the washing and cleansing agents according to the v present inventionwhich are intended for the treatment of textiles, the content-of3.5-bis-(sec. amino)-pyrazine-2.6- dicarboxylic acid amides isadvantageously 0.01 to 5%,

calculated on the weight of the composition." On' the other hand, if itis only desired to attain an improved appearance of the washing andcleansing agent itself, then a content of 0.001 to 0.5% is suflicient.Thus washing and cleansing agents according to the present invention arecharacterised by contents of 0.001 to 5% of 3.5-bis- (sec.amino)-pyrazine-2.6-dicarboxylic acid amide. These optical brighteningagents can be incorporated in the washing and cleansing agents eitheralone or together with other optical brightening agents. Particularly,in all round textile washing agents for household use, the 3.5 bis (sec.amino) pyrazine 2.6 dicarboxylic acid amides which are effective forcertain more hydrophobic fibres or parts thereof such as acyl cellulose,polyamide and polyurethane fibers, as well as for W001 and silk, can

be complemented by optical brightening agents which have affinity tocellulose fibres.

The following examples illustrate the invention. Where not otherwisestated, parts are given as parts by weight. The temperatures are indegrees centigrade. The relationship of parts by weight to parts byvolume is as that of kilogrammes to litres.

Example 1 3.5 bis ethylaminopyrazine-Z.G-dicarboxylicacid-bisethyla-mide of the formula:

212 parts of 1.3-diethyl-4-amino-S-nitroso-uracil and 183 parts of1.3-diethyl-4-amino-uracil are dissolved in 750 parts of glacial aceticacid and the solution is refluxed for 3 hours while stirring. Thegrey-greenish solution is cooled, the precipitate formed is filtered 01funder suction, washed well with water and dried. 320 parts of 3.2;5.6bis [(1'.3' diethyl 2.4 dioxo 1.2.3'.4'- tet-rahydro)-1.4'-pyrimidino]-pyrazine are obtained as white crystals which melt at 233.5234.5. Thiscorresponds to a yield of 89% of the theoretical calculated on the1.3-diethyl-4-amino-S-nitrosouracil used. An analytically purepreparation recrystallised from 75% acetic acid which melts at 235.5236has the following elementary analysis.

Calculated for C H O;N C=53.32%; H=5.59%; N=23.32%. Found: C=53.17%;H=5.61%; N: 23.1 1%

To saponify the3.2;5.6-bis[(1'.3'-diethyl-2'.4-dioxol'.2'.3'.4'-tetrahydro)-1'.4'-pyrimidino] -pyrazine, 10 parts are refluxed for 2 /2 hours with300 parts by volume of 1 N-caustic soda lye and 200 parts of ethanol.The precipitate which crystallises out on cooling is filtered off undersuction, well washed and dried. 7.5 parts of 3.5- bisethylamino-pyrazine-Z.G-dicarboxylic acid bis-ethylamide (M.P. 133-134)are obtained. An analytically pure preparation recrystallised fromethanol, has the same melting point and the following elementaryanalysis.

Calculated forC H O N C =54.52%; H=7.84%; N=27.25%. Found: C=54.63%;H=8.00%; N: 27.21%.

On using the corresponding amounts of 1.3-dipropyl-, 1.3-dibutylandl.3-dimethylP4-amino-uracil and of 1.3- dipropyl, 1.3-dibutyland1.3-dimethyl-4-amino-S-nitrosouracil, the following3.2;5.6-bis-[(1.3'-dialkyl-2'.4'-dioxo- 1.2'.3'.4'-tetrahydro)-1.4'-pyrimidino] -pyrazines are obtained in a similarmanner:

By saponifying these according to paragraph Z the example, thecorresponding 3.S-bis-alkylaminopyrazine-Z.6 dicarboxylicacid-bis-alkylamides are obtained:

1 The crystals contain crystal solvent.

All these 3.S-bis-alkylaminopyrazine-Z.6-dicarboxylicacid-bis-alkylamides have a strong 'to very strong violetbluefluorescence depending on their composition.

Example 2 3propyla1mino-S-ethylamino-pyrazine-Z-carboxylic acidpropylamide-6-carboxylic acid ethylamide of the formula:

CzH5--NHO C2H5-NH-C O 42 parts of 1.3-diethyl 4-amino-5-nitros0-uraciland 42 parts of 1.3-dipropyl-4-amino-uracil are dissolved in 150 partsof glacial acetic acid and the solution is refluxed for 3 hours whilestirring. The pale brownish solution is cooled and diluted with water.The precipitate formed is filtered oif under suction, washed well withwater and dried. parts of 3.2-[(1'.3-diethyl-2.4'-dioxo-1'.2.3'.4'-tetrahydro) 1'.4 pyrimidino] 5.6 [(1.3 dipropyl- 2'.4' dioxo 1.2'.3.4'tetrahydro) 1'.4' pyrimidinolpyrazine are obtained in the form of whitecrystals which melt at 147.5-149. This corresponds to a yield of of thetheoretical, calculated on the 1.3-diethyl-4-amino-5- nitroso-uracilused. An analytically pure product recrystallised from ethanol melts at-151 and has the following elementary analysis. Calculated fOI'CHI-124N604: Found: C=55.70%; H=6.52%.

To saponify the 3.2-[(1.3-diethyl-2.4-dioxo-1.2.3'.4'-

75 tetrahydro) 1'.4 pyrimidine] 5.6 (1'.3' dipropyl- 21.4? dioxo1'.2.3'.4 tetrahyd-ro) 1.4"- pyn'midinolpyrazine, 10parts are refluxedfor 2% hours with 300 parts by volume of 1 N-caustic soda lye and 200parts of. ethanol. The reaction mixture is cooled and then neutralisedwith diluted hydrochloric acid. The precipitate 3 formed is filtered offunder suction, washed and dried. 7.2 parts of 3 propylamino- 5ethylarnino pyrazine; 2.6 dicarboxylic acid 2-propy1amide-d-ethylamidare obtained. M.P.[91-92 t a An analytically pure preparationrecrystallised from ethanol has the following elementary an'alysis.#Calculated for C16H28N602: N=24.98%. Found: C=57.1 4%; H=8.45%; N:24.91%. 7 H I u .On condensing 4-amino-uracils with4-arnino-5-nitrosouracils which are differently alkyl substituted at thering nitrogen atom, for example by using corresponding amounts ofl.3-dimethyl-, 1.3-diethyland 1.3-dipropyl-4- amino-uracilsand.l.3-dimethyl-, 1.3-diethyland 1.3-dipropylf4-aminoJ-nitroso-uracils,the following unsymmetrical3.2;5.6-[(1".3'-dia.lkyl-2.4'-dioxo-1.2'.3'.4.-tetrahydro)-1'.4-pyrimidino]-pyrazines are obtained in the same way: a

The wool is then rinsed and dried in the air. In this Way 7 Example 3 v3.5-bis-methylamino-pyrazine-Z-carboxylic acid-phenyl -amide6-carboxylicacid methylamide of the formula:

31 parts of 1.3-dirnethyl-4-amino-uracil and parts of1.3-dimethyl-4-amino-5-nitroso-uracil are refluxed while Elementaryanalysis, percent 1. Alkyl R1 and Ra i 2. Alkyl R3 M.P.,

and R4 0.

C caid 0 found H cald H found N cal d N found -orrn-Ca'Fl'v 169-1631553.32 53.36 5.59 .5. 57 23.32 23.24 0m 0m. 253-254 50. 60 50. 61 4. s54. 72

On saponifying these according to paragraph 2 of the stirring for 3hours in 200 parts of glacial acetic acid.

above example, the corresponding unsymmetrical 1.3-bis- 5 The reactionmixture is cooled, the precipitate formed isalkylamino-pyrazine-2.6-dicarboxy1ic acid-bis-alkylamides filtered offunder suction, washed well with water and are obtained: dried. 51 partsof 3.2;5.6-bis-[(1'.3'-di-methyl-2'.4-dioxo- V Elementary analysis,percent 1. Alkyl R1 and 2. Alkyl R; 1%.? 7

RI 7 and o cald 0 found Hcald Hfound Ncald Nfound' 2 2 .25 26.9Edi-33:11:11: 138335 ift $123 333 a 3.91 25.98 29.92

' All these unsymmetrical 3.5-bis-alkylamino-pyraz:ine-2.6-1'.2.3'.4'-tetrahydro)-l'.4-pyrimidino] -p yrazine are obdicarboxylicacid-bis-alkylamides have a strong to very tained in the form of whitecrystals which melt at 390 strong violet-blue fluorescence depending ontheir com- (the melting point depends on the heating time). Thisposition. Due to this property, they can be used for the corresponds toa yield of 84% of the theoretical, calculated brightening ,of naturaland synthetic polypeptides as on the 1.3-dimethyl-4-amino-uracil used.Recrystallized follows: from 75% acetic acid, an analytically purepreparation (a) Synthetic polypeptides-50 parts of pale yellowish hasthe following elementary analysis. nylon fabric are washed for 30minutes at 70 in 2500 Calculated for C H O N C=47.4%; H=4.17.%; parts ofa washing liquor containing 6.3 parts of an alkyl- N=27.8%. FOundIC=47.4%; H=3.95%; N=27.6%. aryl sulphonate of the marketed nameSantomerse No. 1 To saponify the3.2;5.6-bis-[(1'.3'-dimethyl-2'.4-dioxoand 0.005 part of3-propylamino-5-methylamino-pyrazine-1'.2'.3.4'-tetrahydro)-l.4'-pyrimidino] pyrazine, 152 2 carboxylicacid-propylamid e-6-carboxylic acid methylparts are refluxed for 6 hourswith a solution consisting amide, The fabric is then rinsed and driedinthe air. The of 200 parts of potassium hydroxide and 2400 parts offibres so treated have a much more white appearance in ethanol. 117parts of 3.5-bis-methylamino-2 carboxyd li ht h t e t d gogds.pyrazine-6-carboxylic acid methylamide (M.P. 214, de- The3-methy1amino-5-ethylamino-pyrazine-2-carboxylic composition dependenton the heating time) are obtained. acid-methylamide-6-carboxylic acidethylamide and 3- Recrystallized from ethanol, an analytically purepreparapropylamino-S-ethylamino-Z carboxylic acid propyltion has thefollowing elementary analysis. amide-G-carboxylic acid ethylamidedescribed in the above Calculated for C H O N /2H O: C=43.48%; examplecan be used in thesame way-with similar suc- .3%- ound: C=43.59%;H=5.50%; cess. N=28.45

(b) WOOL-100 parts of previously bleached wool flan- To amidate the3.5-bis-methylamino-2-carboxypyrazinenet are washed for half an hour at55 in 2000 parts of a 6-carboxylic acid methylamide 20 parts are mixedwith washing, liquor containing 5 parts of an alkylaryl 5111- 150 partsof thionyl chloride. The mixture is left to stand phonate of themarketed name Santomerse No. 1 and for 45 minutes and then the excessthionyl chloride is re- 005 "part of3-propylarnino-5-ethylamino-pyrazine 2 carmoved in thevacuum. Theremaining crystalline acid boxylic acid-propylamide-6-carboxylic acidethylamide. chloride is then slowly added to a solution of 10 parts of 9aniline and 400 parts of abs. pyridine, which solution is cooled with amixture of ice/ sodium chloride and stirred overnight. The pyridine isthen removed by steam distillation, the residue is filtered off undersuction and washed well with water. Pale yellow crystals of3.5-bis-methylamino-pyrazine-2-carboxylic acid phenylamide-G-carboxylicacid methylamide are obtained which melt at 195- 197.

10 N=26.74%. Found: C=57.42%; 26.86%.

Ami-dation of 3.5-bis-methylamino-2-carboxy pyrazine-6-carboxylic acidmethylamide in pyridine or .iii an aqueous medium according to paragraph3 of this example with the amines corresponding to R in the following.table, produces the following compounds:

Recrystallised from ethanol, an analytically pure preparation melts at198198.5 and has the following elemen- 10 s tary analysis. CHa-NHC 0-0-Calculated for c n o N c=s7.31%; N=5.77%; N 3- No. R M.P., 0 Colour offluorescence 2 CH OH OH 5 ii s .NH0Hi..:oHcHa 218 -219' D31 4 'NHCHzOHa197 198.5 D0.

5 Ami-onto 218.5-220 Blue-violet.

10..- NHCH2-1OH=CHQ 194 -195. V 11 NH-(CH -CHz 121 421.2 J D Oi /CHr-C 212. 'NHCH 2 m 237 -23s Blue-violet.

GET-CH3 13 128 129 viOlet.

GHQ-CH3 14"..- NHC 188 -190 Violet-blue.

H-CC-H 15 NHC\ V 223 .224 Blue-violet.

16"... NH-|QH: 204 .205 Violet-blue.

CHa

17...-.. N -Q 211 .-212,5 Blue-violet.

18.--" -NH 19 -195 Do.

21-- NHQ 186 -187 See footnote at end of table.

13' methylarnide, then the following compounds, are obtained:

1 The melting points depend greatly on the heating time.

14 1, 2, 3, 4, 5, 6, 8,10, 11,12, 14,15, 16,19, 20, 21, 22, 23, 24, 25,26, 27, 29, 30, 31, 33, 34, 36, 38, 39, and 41.

(b) W00l.50 parts of previously bleached wool flannel are treated for 1hour at -55" in a dyebath' (liquor ratio 1:20) containing 3 parts ofsodium hydrosulphlte and 1 part of sodium pyrophosphate and also 0.05part of 3.5-bis-methylamino-pyrazine-2-carboxylic acidphenylamide-6-carboxylic acid methylamide. After rinsing and drying, theWool flannel has a considerably more white appearance than materialtreated without the addition of brightening agents.

The following compounds in the above tables can be used in the samemanner with the same success: Nos. 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 12,14, 15, 16, 18, 19, 21, 22, 23, 24, 25, 27, 29, 30, 31, 39, 40 and 41.

(c) Pure silk.10 parts of pale yellowish pure silk are washed at for 30minutes in 200 parts of a washing liquor containing 0.5 part of analkylaryl sulphonate. of the marketed name Santomerse No. 1 and 0.01part of 3.5 -bis-metl1ylamino-pyrazine-Z-carboxylic acidphenylamide-6-carboxylic acid methylamide, and then rinsed and dried inthe air. In this way, pure silk of considerably more white appearance isobtained than if it had been washed without the addition of thebrightening agent named.

Also very beautiful effects areobtained if instead of the brighteningagent used above, the following com- Elementary analysis in percentSubstituent M.P., 1, 2 and s 0.

O cald 0 found H cald H found N cald N found CH2 161-162 69. 3G 69. 305. 39 5.36 14. 9s 15. 06

By amidation in pyridine according to paragraph 3 of this example, thecorresponding 3.5-bis-ethylor -benzyl- 40 aminopyrazine-2-carboxylicacid ethylor benzyl-arnide- 6-carboxylic acid amides are obtained, forexample:

pounds mentioned in the tables are used: Nos. 1, 2, 3, 4, 5, 7, 11, 12,15, 27 and 31.

Sub- Elementary analysis in percent stituent l .P., N0. R1, R2 X C.

and R 0 C H H N N cald found cald' found cald found 40"-.- C2H5 NHC 146.5-147. 5 60.65 60. 77 6.79 7.07 23. 58 23. 55

41 02116 NHC 108 109 5'6. 9 56. 6 6.7 6.7 26.6 26. 6

1F ([311 HO OH 0 Because of their fluorescence and their drawing power,the compounds listed in the examples and the tables can be used withsuccess for the brightening of textile fibres as follows:

(a) Synthetic p0lypeptides.-50 parts ofundyed nylon are washed at 70 forhalf an hour in a washing liquor (liquor ratio 1:20) containing 0.03part of 3.5-bis-rnethylamino pyrazine-Z-carboxylic acid [3methoxyphenylamide]-6-carboxylic acid methylamide and 8 parts of dodecylbenzene sulphonate, and then rinsed and dried. The nylon so treated hasa much more brilliant appearance in daylight than material washedwithout the addition of brightening agent. sulphonate, also othersynthetic washing and cleansing agents such as, for example, fattyalcohol sulphates or oleoyl tauric acid alkali salts etc. can be used.

The following compounds described in the above tables can be used in thesame manner with similar suc- Instead of dodecyl benzeneamide-6-carboxylic acid ethylamide of the formula:

To saponify the 3.2[(1.3-dimethyl-2.4-dioxo-1'.2. 3.4'tetrahydro)l'.4'pyrimidino] 5.6 [(1'.3-diethyl- 2'.4' dioxo-l'.2.3'.4- tetrahydro)1.4' pyrimidinolpyrazine, produced for example as in Example 2, 57 partsof this compound are refluxed for 6 hours with a solution consisting of45 parts of potassium hydroxide and 500 parts of ethanol. The ethanol isdistilled 011?, the reaction mixture is acidified with dilutedhydrochloric acid and 43 parts of 3-methylamino-5-ethylarnino-pyrazine2-carboxylic acid-6-carboxylic acid ethyl amide are isolated. The compoundmelts at 160162 (the melting point cess instead of the brighteningagents mentioned: Nos. depends on the heating time).

and 100 parts of ethanol, which solution has been cooled with a mixtureof ice and sodium chloride. The whole is stirred overnight. Theprecipitate formed is filtered off under suction and washed well withwater. 3-methylamino-5-ethylamino-p-yrazine-Z-carboxylic acid amide-6-earboxylic -acid ethylamide is obtained in the form of pale yellowcrystals which melt at 212-214.

Recrystallised from ethanol, an analytically pure preparation melting at223 -234 has the following elementary analysis. 7

Calculated C11H1302N6: N=3l.56%. Found: C=49.49%; H=6.9 0%; N: 31.88%.

The following 3-methylamino-5-ethylamino-pyrazine-2- carboxylic acidalkylamide-6-carboxylic acidethylamides for example are obtained in thesame manner on amidation with other amines:

propylamide-6-carboxylic acid methylamideor 0.15 part of3-ethylamino-S-methylamino-pyrazine-2.6-dicarboxylic acid ethylamide or0.3 part of 3-pr0pylamino-5-ethylamino-pyrazine 2 carboxylic acidpropylamide-6-carboxylic acid ethylamide or 0.2 part of 3-ethylamino-5-methylamino-pyrazine-Z-carboxylic acid carboxylic acid benzylamide areused, then similar effects are obtained on treating the fibres abovementioned.

Instead of the anion active washing agent described, also thoseconsisting of salts of sulphonic acid esters of ethoxylated fattyalcohols or salts of sulphonic acid esters of alkanol amides of fattyacids can be used.

Example 7 0.05 part of 3.5-bis-rnethylamino-pyrazine-2-carboxylic acidpheny1amide-6-carboxylic acid methylamide are worked into 100 parts ofwashing agent of the composition: dodecyl benzene sulphonate, 15% sodiumlauryl sulphonate, 2% carboxymethyl cellulose, 15% tetrapyrophosphate,20% tripolyphosphate, 22% sodium sulphate and 6% water. a

If nylon or acetate silk is washed at 60 in a washing liquor containing6 parts per litre of the washing agent described, then the fabric has abrilliant appearance.

If, in the above washing agent instead of the pyrazine mentioned, 0.12part of 3.5-bis-ethylamino-pyrazine -2.6- dicarboxylic acid methylamideare used, then the fibres mentioned also have a beautiful appearance.

It the Washing agent contains 0.15 part of 3.5-bis- Elementary analysisin percent Alkyl M.P., 0.

O cald 0 found H cald l H found N cald l N found C2Hs 162-164 53. 04 53.06 7. 53 7. 59 28. 55 28. 53 --O3H 84- 86 53.3 53.4 7.85 7. 93 26.7 26.8

CH,C 87- 89 59. 6 59. 3 6. 86 6.68 23. 2 23. 4

0.075 part of 3.5-bis-methylamino-pyrazine-Z-carboxylicacid-phenylarnide-6-carboxylic acid methylamide are worked into 100parts of soap powder consisting of the sodium salt of fatty acids with5% water content. Nylon fabric washed at in a Washing liquor (liquorratio 1:30) containing 5 parts per litre of the soap powder describedabove, has a much more brilliant appearance.

If, in the above washing agent, 0.09 part of3.5-bismethylamino-pyrazine-2.6-dicarboxylic acid methylamide are usedinstead of the pyrazine named, then the treated fibres also have abeautiful white appearance. If an even stronger brightening effect onacetate silk is required, then 1 to 2 parts of the brightening agentnamed can be used.

Example 6 0.075 part of 3.5-bis-methylamino-pyrazine-Z-carboxylic acidphenylamide-6-carboxylic acid methylamide' are worked into 100 parts ofwashing agent consisting of 55% sodium salt of lauryl alcohol sulphate,40% sodium sulphate, 2% carboxymethyl cellulose and 3% water content.

Wool, as well as nylon and acetate silk fabric, which is washed at 40-50in a washing liquor (liquor ratio 1:30) containing 5 parts per litre ofthe washing agent described above, has a beautiful white appearance.

If,'instead of the pyrazine in the above anion active washing agent, 0.2part of 3.5-bis-methylamino-pyrazine- 2.6-dicarboxylic acid methylamideor 0.2 part of 3- 'propylamino 5 methylamino-pyrazine-2-carboxylic acidmethylamino-pyrazine-2-carboxylic acid pyridylamide-6- carboxylic acidmethyl amide, then wool flannel or acetate silk washed therein has abeautiful white appearance.

Example 8 0.2 part of 3.5-bis-methylamino-pyrazine-Z.6-dicarboxylic acidmethylamide are incorporated into 100 parts of washing agent consistingof 45% soap, 5% water glass, 10% pyrophosphate, 15 sodium carbonate, 3%mag-v nesium meta silicate, 7% perborate and 15 water.

Nylon and-acetate silk fabric which are washed at in a washing liquor(liquor ratio 1:30) containing 8 parts per litre of the above washingagent have a much more white appearance than when washed Without theaddition of the brightening agent.

If in the above washing agent, instead of the brightening agent named,0.06 part of 3.5-bis-methylamino pyrazine-Z-carboxylic acidpyridylamide-6-carboxylic acid methylamide or 0.04 part of3.5-bis-methylaminopyrazine-Z-carboxylic acid phenylarnide 6-carboxylicacid methylamide, are used then similar effects on the above mentionedfibres are obtained.

Example 9 0.1 part of 3.S-bis-ethylamino-pyrazine-2.6-dicarboxylic acidethylamide are incorporated into parts of washing agent of thecomposition: 12% dodecyl benzene sulphonate, 10% sodium lauryl sulphate,5% Water glass, 2% carboxymethyl cellulose, 15% tripolyphosphate, 20%pyrophosphate, 10% sodium carbonate, 20% sodium Sulphate and 6% water.

Nylon fabric which is washed at 70 in a washing liquor (liquor ratio1:30) containing 8 parts per litre of the ethylamide-6- 17 washing agentdescribed above, has a brilliant appearance.

If, in the above washing agent, instead of the pyrazine Example 10 0.1part of 3.S-bis-methylamino-pyrazine-2-carboxylic acidphenylamide-6-carboxylic acid methylamide are added to 100 parts ofwashing agent consisting of 30% of a condensation product of oleic acidand methyl taurine, 65% sodium sulphate and 5% water.

Nylon fabric washed at 50 in a washing liquor containing 5 parts perlitre of the washing agent described has a much more white appearancethan fabric washed without the addition of brightening agent.

Acetate silk fabric washed under the same conditions with a washingagent of the same composition but containing 0.15 part of3.5-bis-ethylamino-pyrazine-2.6-dicarboxylic acid ethylamide instead ofthe pyrazine named, also has a beautiful white appearance.

Also a washing agent consisting of the condensation product of oleicacid and taurine can be used instead of that desired.

Example 11 0.075 part of 3-ethylamino-5-methylamino-pyrazine-2.6-dicarboxylic acid ethylamide are incorporated into 100 parts ofwashing agent consisting of 25% of a sulphonated condensation product ofp-methoxyphenyl diguanide and oleic acid (1-p-methoxy-phenyl-2-imino-4-amino-6-o1eyl-1.3.5-triazine sulphonic acid), 70% sodium sulphate and 5%water.

Nylon fabric washed at 50 in a washing liquor (liquor ratio 1:30) whichcontains 5 parts per litre of the washing agent described above, has abrilliant appearance.

Wool fabric washed under the same conditions with the above washingagent but containing 0.15 part of 3.5-bis-ethylamino-pyrazinc-Z.6-dicarboxylic acid ethylamide instead of thepyrazine named, also has a very beautiful white appearance.

A beautiful brightening effect on acetate silk is obtained if, in theWashing agent described above, 0.075 part of3.S-bis-methylamino-pyrazine-2-carboxylic acid phenylamide-6-carboxylicacid ethylamide are used instead of the pyrazine mentioned.

What we claim is:

1. A detergent composition consisting essentially of a water soluble,synthetic, organic anion-active detergent selected from the groupconsisting of Water soluble soaps and synthetic, organic non-soap anionactive sulphated detergents, containing 0.001 to 5% by weight, of thecomposition, of a 3.S-bis-diamino-pyrazine-Z.6-dicarboxylic acid diamideof the general formula:

wherein R R and R each represents a member selected from the groupconsisting of lower alkyl and phenyl substituted methyl radicals and Xrepresents a member selected from the group consisting of primary amino,secondary amino and tertiary amino groups.

2. A detergent composition consisting essentially of a water soluble,synthetic, organic anion active detergent selected from the groupconsisting of water soluble soaps and synthetic, organic non-soap anionactive sulphated 18 position, of the3.S-diamino-pyrazine-Z.6-dicarboxylic acid diamide of the formula:

3. A detergent composition consisting essentially of a water soluble,synthetic, organic anion active detergent selected from the groupconsisting of Water soluble soaps and synhetic, organic non-soap anionactive sulphated detergents, containing 0.001 to 5% by Weight, of thecomposition, of the 3.5-diamino-pyraZine-2.6-dicarboxylic acid diamideof the formula:

4. A detergent composition consisting essentially of a water soluble,synthetic, organic anion active detergent selected from the groupconsisting of water soluble soaps and synthetic, organic non-soap anionactive sulphated detergents, containing 0.001 to 5% by weight, of thecomposition, of the 3.5-diarnino-pyrazine-2.6-dicarboxylic acid diamideof the formula:

5. A detergent composition consisting essentially of a water soluble,synthetic, organic anion active detergent selected from the groupconsisting of water soluble soaps and synthetic, organic non-soap anionactive sulphated detergents, containing 0.001 to 5% by Weight, of thecomposition, of the 3.5-diamino-pyrazine-2.G-dicarboxylic acid diamideof the formula:

6. A detergent composition consisting essentially of a water soluble,synthetic, organic anion active detergent selected from the groupconsisting of water soluble soaps and synthetic organic non-soap anionactive sulphated detergents, containing 0.001 to 5% by weight, of thecomposition, of the 3.5-diamino-pyrazine-2.6-dicarboxy1ic acid diamideof the formula:

7. A detergent composition consisting essentially of a water soluble,synthetic, organic anion active detergent selected from the groupconsisting of water soluble soaps and synthetic, organic non-soap'anionactive sulphated detergents, containing 0.001 to 5% by weight, of thecomposition, of the 3.S-diamino-pyrazine-Z.6-dicanboxylic acid diamideof the formula:

8. A detergent composition consisting essentially of a 1 water soluble,synthetic, organic anion active detergent selected from the groupconsisting of water soluble soaps and synthetic, organic non-soap anionactive sulphated detergents, containing 0.001 to 5% by weight, of thecomposition, of, the 3,.5-diamino-pyra ine-2.6-dicanboxylic 75 aciddiamide of the formula:

9. A detergent composition consisting essentially of a water soluble,synthetic, organic anion active detergent selected from the groupconsisting of water soluble soaps andsynthetic, organic non-soap anionactive sulphated detergents, containing 0.001 to 5% by Weight, of thecomposition, of the 3.S-diamino-pyiazine-Z.6-dicarboxy1ic acid diamideof the'formula:

References Cited in the file of this patent OTHER REFERENCES Raybin:Chemical Abstracts, v01. 39 (1945), 4433 Taylor: Chemical Abstracts,vol. 49 and 6967c.

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A WATER SOLUBLE,SYNTHETIC, ORGANIC ANION-ACTIVE DETERGENT SELECTED FROM THE GROUPCONSISTING OF WATER SOLUBLE SOAPS AND SYNTHETIC, ORGANIC NON-SOAP ANIONACTIVE SULPHATED DETERGENTS, CONTAINING 0.001 TO 5% BY WEIGHT, OF THECOMPOSITION, OF A 3-5-BIS-DIAMINO-PYRAZINE-2.6-DICARBOXYLIC ACID DIAMIDEOF THE GENERAL FORMULA: